Resin-forming compositions containing amine salts of sulfonic acids



Patented Aug. 24, 1954 RESIN-FORMING COMPOSITIONS CONTAIN- ING AMINE SALTS OF SULFONIC ACIDS Hans Dannenberg, Berkeley, Calif,, assignor to ShellDevelopment Company, Emcryville, Calif., a corporation of Delaware No Drawing. Application September 21, 1951, Serial No. 247,757

1 This invention relates. toa new composition of matter-which may be used asa film-forming ma.- terial t v produce protectiv coatin s. com:

position is. particularly useful in that, althoughcontaining reactive components, it ha excellent storage Stability and long shelf life," but upon being heated as a film or otherwise, it cures to a hard tough solvent-resistant resinous material. In brief, the composition of the invention is a neutral amine-salt of a sulfonic acid in admixture with a mixture of glycidyl polyether of a poly-. hydric phenol hav n LZ-e oXy quivalency greater than 1.0 and a convertible urea-formaldehyde condensate. The composition is very stable and does. not resinify upon storage over extended periods of time at ordinary temperature. However; upon being heated to above about 100 C., the composition undergoes resinificationto a hard tough product which is insoluble in organic solvents such as methyl ethyl. ketone,

T lycidylp lyether of dihydric phenol. emplcy d in the mixture o r sinsformine mat rial of the. invention. is obtainable by reacting epichlorhydrin with a dihydrio phenol in alkaline medium. The. polyethers are preparedv by heatz oiaonz-o%a-o-om-onmnomw) wherein n is an integer of the series 0, 1, 2, 3 and'l-t' represents the divalent hydrocarbon radical ofthedihydric phenol. While for any single molecule, of the polyether n is an integer, the fact that the obtained pclyether is a mixture of compounds causes the determinedvalue for 11.. e.g., from molecular weight measurement, to began average which is not necessarily 0 or a whole number. Although the polyether is a substance primarily for the above formula, it may contain some material with one or both of the terminal glycidyl radicals inhydrated form.

The simplest polyether is a diglycidyl diether or the dihydric phenol which contains a single diva-lent aromatic hydrocarbon radical from the dihydric phenol and has two. glycidyl radicals 9. Claims. (01. 26045'.2)

linked thereto by ethereal oxygen atoms. More generally, the polyether i of more complex character and contains two or more aromatic hydrocarbon radicals alternating With glyceryl groups in a chain which are linked together by intervening ethereal oxygen atoms, the terminal groups being glyceryl groups, which are mostly glycidyl radicals.

The glycidyl polyethers of a dihydric phenol used in the invention have a 1,2-epoxy equivalency greater than 1.0. By the epoxy equivalency, reference is made to the average number of 1,2-epoxy groups contained in the average molecule of the glycidyl ether. Owing to the method of preparation of the glycidyl polyethers and the fact that they are ordinarily a mixture of chemical compounds havingom what i fer n mole ular W hts n contain om ompounds wh rein th t rmina glycidyl radicals are in hydrated form, the epoxy equivalency'of the product is not necessarily the integer 2. However, in all cases it is a value eater than 1. The l,2..-ep xy qu valency of the polyethers is thusa valuebetween 1.0 and 2,0.

The 1,2-epoxide value of the glycidyl polyether is determined by heating a weighed sample of the ether with an excess of 0.2 N pyridinium chloride in chloroform solution at the boiling point under reflux for 2 hours whereby the pyridinium chloride hydrochlorinates the epoxy groups to chlorhydrin groups. After cooling, the excess pyridinium chloride is back-titrated with 0.1 N sodium hydroxide in methanol to the phenolphthalein end point. This method is used f r obtainin all epoxide values discussed er n- Any of the various dihydric phenols is used in preparing the polyethers including mononuclear phenols such as resorcinol, catechol, hydroquinone, methyl resorcinol, etc; or polynuclear phenols like 2,2-bis(4hydroxyphenyl) propane which is herein termed bis-phenol for convenience, 4,4edihydroxybenzophenone, bis(4-hy, droxyphenyhmethane, 1,1 bis(4 hydroxys phenyDethane, 1,1 bis(4 hydroxyphenyDisobutane, 2,2 bis 4 hydroxyphenyl) butane, 2,2 bis 4 hydroxy 2 methylphenyl) propane, 2,2 9 bis(4 hydroxy 2 tertiarybutylphenyl)- propane, 2,2 bis 2 hydroxynaphthyl)pentane, 1,5edihydroxynaphthalene, etc.

Preferred polyethers used in the process are prepared from 2,2-bis(4-hydroxyphenyl)propane. They contain a chain of alternating glyceryl and 2,2-bis(4-phenylene) propane radicals separated by intervening ethereal oxygen atoms, have a 1,2-epoxy equivalency between 1.0 and 2.0, and have a molecular weight of about 1200 to 4000. More generally, it is preferred to employ glycidyl polyether of a dihydric phenol which has a value for n in the above-mentioned structural formula of about 6 to 15.

The glycidyl polyethers will be mode fully understood from consideration of the following described preparations and the properties of the products.

POLYETHER A In a vessel fitted with an agitator, 223 parts (1 mol) of bispheno1 and 55 parts (1.37 mole) sodium hydroxide as a 10% aqueous solution are introduced and heated to about 45 C. whereupon 113 parts (122 mols) of epichlorhydrin are added rapidly while agitating the mixture. The temperature ofthe mixture is then gradually increased and maintained at about 95 C. for 80 minutes. The mixture separates into a twophase system and the aqueous layer is drawn ofi from the taify-like product which forms. The latter is washed with hot water while molten until the wash water is neutral to litmus. The product is then drained and dried by heating to a final temperature of 130 C. The softening point of the resulting glycidyl polyether is 98 C. by Durrans Mercury method. The molecular weight of the product is 1400 as measured ebullioscopically in ethylene dichloride, and it has an epoxide value of 0.103 equivalents epoxy per 100 grams. It will be identified hereinafter as polyether A.

POLYETI-IER. B

This polyether is prepared as described for polyether D except that the 100 parts of polyether A are mixed, heated and reacted with 7.75 parts 1 of bis-phenol. The resulting product has a softening point of 156 C., a molecular weight of 3750, and an epoxide value of 0.036 equivalents epoxy per 100 grams.

The properties of the foregoing polyethers are summarized in the following table:

Epoxy Softening Mol. 1,2epoxy Polyether n Value,

Point, C. Wt. GIL/100 Equivalency A 98 1, 400 3. 74 0. 103 l. 46 B 131 2, 900 9. 02 0. 1.45 O 156 3, 750 12. 00 0. 036 l. 40

The convertible urea-formaldehyde condensate used in admixture with the glycidyl polyether is one obtained in known manner. It is a material which is soluble in organic solvents and capable of being converted to a form which is insoluble in such solvents. A condensate particularly suitgroups.

ed for use in the invention is what will be termed an alkylated urea-formaldehyde condensate, by which term reference is made to urea-formaldehyde condensates containing substituentfgroups from alcohols. These alkylated urea-formaldehyde condensates are prepared by reacting formaldehyde with urea and an alcohol in the presence of an acid, or by first reacting urea with formaldehyde in alkaline medium so that a methylol urea is formed and then reacting this product with alcohol in an acid medium. Well suited for use in the invention are those alkylated urea-formaldehyde condensates derived from saturated aliphatic alcohols of 2 to 8 carbon atoms, and particularly suited is the butylated urea-formaldehyde condensate obtained from nbutyl alcohol. These alkylated urea-formaldehyde condensates are soluble in various organic solvents including n-butyl alcohol. Preparation of the condensates will not be reiterated here in detail since they have been repeatedly described in the rior art and the preparation is adequately disclosed in Patent Nos. 2,222,506; 2,226,518; 2,227,223; 2,322,979; 2,327,984; 2,323,357; 2,325,- 265; and 2,350,894.

The proportions of the two components in the mixture of the glycidyl polyether and urea-formaldehyde condensate can be varied widely. A desirable weight ratio of glycidyl polyether to ureaformaldehyde condensate is from about 90:10 to 30:70, but the invention is not limited to such a range of ratios. A more preferred range is from about 85:15 to :40, i. e., a mixture containing about 15 to 40% of the urea-formaldehyde condensate. Products having excellent properties are obtained with a mixture containing about 30% urea-formaldehyde condensate and about glycidyl polyether.

The amine salt of a sulfonic acid which functions as a heat-activated curing agent for the resin-forming components in the composition of the invention is obtained by simply neutralizing the sulfonic acid with an amine. It appears that any amine which will give a neutral salt with the sulfonic acid is suitable. The amine contains one or more primary, secondary and/or tertiary amino groups, and is preferably free of other acid and basic acting groups. Representative amines include such compounds as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, triethanolamine, 2-chlorethylamine, diisopropylamine, hexylamine, diethylenetriamine, cetyldimethylamine, nonylamine, hexamethylenediamine, morpholine, 2,6-dimethylmorpholine, N- butylmorpholine, N,N-dimethylmorpholine, aniline, benzylamine, benzyldimethylamine, chloraniline, pyrrole, pyridine, piperidine, pyrimidine, piperazine and the like.

The organic sulfonic acids which are employed as amine salts in the invention have the sulfonic acid group or groups linked to aliphatic, aromatic, or alicyclic hydrocarbon radicals, which radicals are preferably free of other basic and acid acting They include, for example, aliphatic monosulfonic acids such as methanesulfonic acid. ethanesulfonic acid, propane-l-sulfonic acid, propane-2-sulfonic acid, butane-l-sulfonic acid, 2-methylpropane-l-sulfonic acid, butane-2-sulfonic acid, hexane-l-sulfonic acid, decane-lsulfonic acid, dodecane 1 sulfonic acid, hexadecane 1 sulfonic acid, ethanesulfonic acid, propene 2 sulfonic acid, 2 methylpropene-Zlsulfonic acid, and diisobutylenesulfonic acid; the aliphatic polysulfonic acids such as methaccuses fonicacid, naphthaline z sul'fonic:acid, 2,"ie; -tri methylsulfonicacid, benzyl'sulfonic acid; phenyl ethanesulfonic acid, 1-phenylethene-2-sulf'onic; acid, mesitylenesulfonic acid; andm-cymenesulfoni'c acid"; the aromatic'pol'ysulfonicacids such asm-benzenedisulfonic acid, p benzenedisulionic: acid, benzene-1,3;5-trisulfbnic acid, andtoluene 2,4-disulfonicacid; and the alicyclic sultoni'c: acids such as cyclopentanesulfonicacid and cyclehexanesulfonic acid.

The salts are-prepared by. simple-neutralization of the sulfonic acidwith the amine: For example, a particularly preferred salt, morpholinium p. toluenesulfonate, is prepared asfi'illows: Thirty grams of p-toluenesulfonic acid monohydrate aredissolved: in. 60 grams of. acetone and the sol.u= tion placed in an ice bath. Approximately 1 6 grams of morpholine are added slowlywith-stir ring so the temperature does not exceed I 5? C. A very small excess of morpholine is employed'soz that the mixture is slightly alkaline toindi'cator paper. Crystalsof salt formimmediately, are-re moved by filtration, washed with cold acetone. and recrystallized from boilingz acetone (about. 1 0} ml. per gram of salt). Themecrystallized saltuis filtered after cooling in ice water and dried at. room temperature. A. second: crop isobtainedi by drying the mother liquor with. anhydrous cal-- cium sulfate and concentrating in vacuo; a: third. crop. by evaporating, in vacuo, thezmother-liquor from the second crop to dryness. The crystals. thus obtained are likewise purified by recrystallization and a total of 27.5 grams-of salt obtained. The melting point of; the salt is 126 C. For general use in varnishes, enamels and the like;,. it is not-necessary to prepare the crystalline salt. A- solution of the salt in a solvent consisting of equal parts by weight of xylene and n-butyl. ale cohol is easily obtained by'neutralizing a solution of sulfonic acid in the solvent with the; amine.

The salt employed is neutral; in the sense that it is neither acid nor basic because the presence. of unneutralized acidic or basic. groups; therein adversely affects the stability againstgelation of" the-composition of the'inventionr Thus in. preparing. thesalt. ofdiethylamine and m-benzenedisulfonic acid,,there. is used 2 mols of.- the-:amine per mol. of the acid. Likewise, inpreparinga the salt of. ethylenediamine and p-toluenesulfonic acid, there is used. 1. mol. of. amine: with 2. mols of acid. Although it is preferred to employ salts of amines free of other acid or basic acting groups than the amino group and sulfon-ic acids free of other acid or basic acting groups than the sulfonic acid group, the amine andyor sulfonic acid may containsuch other acidic-and/or basic groups since neutrali salts are employed. Thus there may be used the neutral salt of butylamine and sulfoacetic acid prepared by neutralizing, 1 molof the acidiwith 2.1nols of the amine.

The salts are used in smallproportions; in the composition of' the invention since they have: powerful catalytic activity which is; brought into action by heating. Ordinarily, about 0.5; to 2% by'weightof salt based-upon the combinedweight: o1 theglycidyl polyether and the urea-aldehyde.

6' condensateisemployed. be. extended, especial-1y though this is usuallyon the upper side, alavoided because of increased cost and lack of necessity. Thus there may be used from about 0.1 to 10% as well: as higher percentages.

The composition of the invention is prepared by mixing together the three components thereof. This is conveniently accomplished in a solvent. A variety of substances: are suitable for this purpose including ketones such as acetone,

methyl ethyl ketone, methyl isobutyl ketone, iso-s phorone, etc.; ether alcohols; such as methyl, ethyl or butyl ether of ethylene glycol or d iethyl ene glycol; and chlorinated solvents, such as tri chloropropane, chlorofor etc. T'osaveoxpense, these active solvents are ordinarily used in ad mixture with diluents which are themselves not solvents when used alone, but which may be in-- corporated with active solvents. Reference is. made to aromatic hydrocarbons; such as benzene, toluene, xylene, aromatic petroleum thinnenetc; and alcohols such as ethyl; isopropyl and n-butyl alcohol. In order to achieve desired evaporation and drying characteristics, the-solvents are com bined and balanced for desired properties: in the manner well known in the. lacquer and varnish arts. Typical solvent combinations. are illustrated in examples given hereinafter;

With some of the salts which have fewer car-' bon atoms, trouble is obtaining complete solution thereof in solutionsof the composition. Thisv is readily overcome by including about 0.2 to 1 of water therein. The diificulty may also be avo'ded by employing salts having high ratios of carbon atomstoaminesulfonate salt groups as is the case with the salt of cetyl amine salt and dodecylbenzenesulfonic acid.

Solventefree compositionssuitable. for. molding. operations. and the. like may be obtained. by evaporating. the. solvent from the obtained solutions. The evaporation is effected. at. a. temperature. below that which activates. the. salt curing catalyst, and. thus, premature gelation. is. avoided. A temperature below about C. is usually satisfactory for this purpose.

The composition of. the invention. cures. to a hard resinous material in short time upon being; heatedtoatemperature above. about 0. Ex cellent cure. is obtained at about. 1505 and satisfactory cure may be. obtained. within. the range. oi aboutv to. 250 C. provided the time of. heating. is. correlated with. the tempera.- ture. Complete. cure: is. obtained. in about. one minute's time. at .230. C.,, but. an. hour may be required at. 125. C. with use. of about-1%- of the. preterred salt, morpholinium p-toluenesulionate...

The resulting cured resinous product hard and tough, and has outstanding resistance against the deteriorating and destructive action of alkalies; The cured resinous products of the invention are thus of. great value as surface coating films for protection. offmeta'l' surfaces which come into repeated. contact with alkaline materials such as soapy water, as is the case with washing machines; By'use of propertime and temperature in? curing, the obtained resinous product has a very tight cure and insolubility in all non-destructive solvents such as. methyl ethyl ketone, for' example.

When: used as: film-forming; materials which may be applied by brushing, spraying and the like, the compositions. containing the glycidyl polyether, the urea condensate and salt catalyst However, the range may occasionally encountered 7. may also contain various other materials such as pigments, plasticizers, and other resins. Pigments such as titanium dioxide, antimony oxide, lead oxide, carbon black, chrome-yellow, zine there was present 0.2, 0.5 and 1.0 part of'salt per 100 parts of resin-forming material (the polyether plus the urea resin). Metal panels were coated with the solutions containing the salt with use oxide, para red, and the like, are used in the of cold-rolled steel sheeting (24 gauge) and a compositions. Best results in preparing enamels Fischer-Payne dip coater operated at a speed of 2 are obtained by grinding the pigment with a porinches per minute. After an air-drying period of tion of the solvent and urea condensate and then at least 30 minutes, the panels were baked for 30 adding the remainder of the solvent and glycidylminutes in an air oven at the temperatures listed polyether after the grinding operation. The in Table II below. The films were about 0.5 mil enamel is ready for application after addition of thick. the curing catalyst. In order to determine the extent of cure and With eithervarnishes or enamels of the invencharacter of the resinous films, the coatings were tion, thick layers of the film-forming material separately subjected to a test with methyl ethyl may be applied to a surface such as metal, wood, ketone (MEK test), this ketone being a solvent or the like. Curing completely therethrough is for uncured films, and a test with boiling water attained because the conversion to an insoluble (boiling H2O test). The MEK test was per-- film is not dependent upon contact with air. This formed by placing a drop of methyl ethyl ketone fact also makes the compositions valuable in on the coating and scratching the exposed portion manufacture of laminates wherein the laminae of film with a sharpened pencil point (grade F). are cloth, paper, glass-cloth, and the like. Such A well-cured film resisted damaging effect of the laminae are impregnated with a solution of the pencil point applied with moderate finger presglycidyl polyether and curing catalyst. After sure. Incompletely converted films showed varydrying, the impregnated sheets are stacked and ing extents of swelling, softening or dissolving cure is efiected in a heated press. and becoming sticky. A rating system was em- Many of the compositions arealso suitable for ployed as indicated in Table I below. molding operations wherein they are introduced The boiling H2O test was performed by immersinto a mold, compressed and cure completed with ing the coatings in boiling water, and after coolheat. Various fillers, dyes and pigments may be ing, inspecting them in two respects, the extent incorporated with the compositions in use for of whitening of the film and the adherence of the molding operations such as wood flour, talc, film to the substrate. A rating system was emalphacellulose, zinc sulfide, etc. ployed, as given in Table I, to record both indi- The following examples are given to illustrate cations. Under boiling H2O test in Table II, the the invention, but they are not to be construed first number refers to the extent of whitening as limitative thereof. The parts and percentages 3 and the second to the adherence. Thus the symare by weight. bol 8-10 means a slight whitening and no loss of EXAMPLE 1 adhesion. Stock solutions were prepared containing polyf ghese Same ratings are used m the example to ether B or polyether C in admixture with butylo T W I ated urea-formaldehyde resin, obtained by cone densing urea with formaldehyde in the presence of n-butyl alcohol. A commercial solution was Boiling H2O Test used containing butylated urea-formalde- Rating MEK Test hyde resin in a :40 weight ratio of n-butyl alwhitening Adhesim cohol and xylene. The stock solutions were pre- 45 paged so 1 to contajin total of about 375% 09::1 Unchanged." No whitening No loss of adhesion. resin-formmg material therein w1th use of a s solvent containing equal parts by weight of xylene lisofiened Hazy to muky Bnstering and Cellosolve acetate (ethylene glycol mono- 369mm)- Stock Solution I contained polyether 59 IIII}Part1 so1ub1e Milky to 0111110.... Film 100501100. B and the urea resin in a weight ratio of :30. 2 Stock solution 11 contained the same ingredients 1 soluble White Fflmremwed' in a weight ratio of :20. Stock solution III contained polyether C and the urea resin in a The m Obtamed W hard smooth and F weight ratio of 170130 While Stock solution v 55 of cratering or crawling. The results obtained o tai d th same ingredients i a weight ratio with the two tests described above are listed in of 80:20. A 10% solution of the morpholine salt Tabl II fo wi w r the l t d t mp raof p-toluenesulfonic acid was prepared and added tures are the temperatures of bake for effecting to three portions of each stock solution so that cure of the films on the panels.

Table II Added MEK Test Boiling 1110 Test Stock Solution Percent 0. 2 s 10 10 10 10 0-0 0-10 8-10 10-10 10-10 0.5 3 10 10 10 10 00 10-10 10-10 10-10 10-10 1.0 4 10 10 10 10 0-0 10-10 10-10 10-10 10 10 0.2 1 9 10 10 10 4-4 8-10 8-10 10-10 10-10 0.5 e 10 10 10 10 0-1 3-10 10-10 10-10 10-10 1.0 4 10 10 10 10 4-8 0-10 10-10 10-10 10-10 0.2 4 10 10 10 10 0-1 0-10 10-10 10-10 10-10 0.5 7 10 10 10 10 1-0 10-10 10-10 10-10 10-10 1.0 0 10 10 10 10 00 10-10 10-10 10-10 10-10 0.2 1 s 10 10 10 0-0 0-8 0-10 8-10 8-8 0.5 0 10 10 10 10 1-0 8-8 10-10 108 0-0 1.0 s 10 10 10 10 1-0 8-8 10-10 10-10 0-0 The compositions of the invention as well as solutions thereof have excellent storage stability. When stored at ordinary temperature, they are .10 To a portion of ,the enamel base was added 0.82 part of the pyridine salt of p-toluenesulionic acid per 100 parts of resin-forming material (the polyether plus the urea resin). A filmof the "resistant against gelation and resinification in- 5 enamel f had Stood. tempemture for definitely. Data on this point will be given in g p f this example, the storage stability being judged steel p auqwed an f m of by measurement of viscosity according to the the solvent, and then baked in an air .oven for 30 GardnepHoldt scale. minutes'at-ltlo C. A hard :toughcured iilmw-as Two of the stock solutions containing .the mor- 10 t ase'vldenced having a rating 10 pholine salt of p-toluenesulfonic acid described E' P' in Example 1 were stored at room temperature Anothe enamel base of about 20C. to 25 C. The first of these was i 'morpholme pmiuenesuhwc the composition withstock solutionI having an acld per of resmformmg mammal added 1% of the Salt therein The initial added theieto. This .enamel was also .coated on a sheet steel panel, and after an drying, was cosity was G, and after 42 :days storage, the VIS- b d f 30' t at 150 C Th cosity had increased only slightly toi'between G 6 es o g f? mg and When a total of 133 days had passed ossy tough n on also had .a rating .of 10 by the :(over v5 monthstime) the viscosity had increased EXAMPLE 4 toibetween I and J.

The other was the composition with stock so- .A stock u on was p p e c ng lut'ion 111 containing the added 1% of the salt, a of p ly t r B nd 30 parts f b tyl t whichcomposition had an initial viscosity of .l t o fm d h d resin (from B t -8 After 29 days time, the viscosity was between L -d ss e i fiP of fiellosolvo acetate, 11 and M. Thecompositi0n had a viscosity of only ofxy e nd 11 parts of n-butylalcohql- T por- T after days stgraga tions of the stock solution,-there-was added *llpart In contrast to the stable compositions noted 9 h lle t salts listed in Table below P -'above, the same compositions containing like 90 .na ts of momo n m er a h P percentages 'of the free p-toluenesulfonic-acid in fi l-1 6 P1115 rea 11 5 1 th .fi be a d place of its-salt will gel in a few minutes time. 1 5. 0% lut on n e t e .n-b tyl acetate o -A-solutionwas also preparedcontaining about mix ure f ql al Weight of -bllfi l .al q q and 85 parts polyether C and 15 parts 'of butylated xyl n Metal panels of sheet steel were dip urea formaldehyde 'resin in about 113 parts of coated wit the so u onsa des r bed i .Exan methyl isobutyl ketone, 75 parts of toluene, '63 ple 1,,.al1. W d to air dry I ratleastBO mi u es parts-of Cellosolve acetate, G-partsof xylene and and thenba fo 30 mi ute .i an air oven at 9 parts of normal buty alcohol to which was the temperatur s give .1 b eIII. The resultadded about 2 parts of the neutral salt from 1 :ing panels were-subjectedto the M EKtestand the mol of m-benzenedisulfonic-acid and 2 mols of boiling-H2O test with the following results.

Table III composition f Salt Ft om g g g 33ml; lfilggilfilrfigst 120 10 o A Agg an t lu n 8:13 a 00 10 .9 0 i 23 18 18 2B iiitttiiitl-f 1 53; t g- 333 as .t as 9215523123333? P 553. ,}g 13 l 18' ttfillli ltidi 1 3g; n I v w Mtttfitid. l gg 53 triethylamine. The initial viscosity of the solution was between J and K. After storage for '7 EXAMPLE 5 days time at room temperature, the viscosity was Several f the compositions d sc bed in EX- unchanged. Upon replacing the 2 parts of salt ample 4 were stored at room temperature of about with a like amount of free m-benzenedisulfonic 20 C. to 25 C. to determine their storage staacid, the solution gelled almost immediately. bility. They did not gel and underwent to change Upon reducing the amount of free acid to only except for a small increase in viscosity as indi- 0.25 parts, the solution gelled within 4 hours. 5 cated in Table IV.

EXAMPLE 3 Table IV An enamel base was prepared containing 409 parts of titanium dioxide pigment (Rutile T102) 0 t1 Gardner'mldt Vlsmslty After dispersed in 400 parts of polyether A and 100 Ompw parts of butylated urea-formaldehyde resin (from 1mm] 30 Days 3 Beetle 227-8) in a solvent mixture consisting of B G G I L 315 parts of Cellosolve acetate, 355 parts of xylene H H I J and 60 parts of n-butyl alcohol, and the mixture H I H J was pebble milled for 56 hours.

1 1 EXAMPLE 6 The neutral salt of cetyldimethylamine and mixed C1-C3 alkanesulfonic acids (Indoil Chemical Products) was employed in the example. To a portion of the stock solution described in Example 5, 1 part of the salt per 100 parts of resinforming materials was added, the salt being introduced as 25% solution in Cellosolve acetate. A sheet steel panel was dip coated in the solution, allowed to air dry for about 30 minutes, and then was baked in an air oven for 30 minutes at 140 C. Complete cure was obtained as was indicated by a rating of 10 by the MEK test.

I claim as my invention:

1. A composition adapted to cure to a hard resinous product upon being heated to a temperature above about 100 C. which comprises a mixture of glycidyl polyether of a polyhydric phenol having a 1,2-epoxy equivalency greater H than 1.0 and a convertible urea-formaldehyde condensate in admixture with a small amount of a neutral salt of an amine and a sulfonic acid, said amine being a member of the group consisting of morpholine, triethylamine, pyridine, aniline, diisopropylamine, diethylamine and cetyldimethylamine.

2. A composition which comprises a mixture of glycidyl polyether of a dihydric phenol having a 1,2-epoxy equivalency between 1.0 and 2.0 and a convertible alkylated urea-formaldehyde condensate soluble in n-butyl alcohol in admixture with about an added 0.2 to 5% by weight of a neutral salt of an amine and a sulfonic acid, the composition containing a weight ratio of said polyether to said condensate of from about 90:10 to 30:70, said amine being a member of the group consisting of morpholine, triethylamine, pyridine, aniline, diisopropylamine, diethylamine and cetyldimethylamine.

3. A composition which comprises a mixture of glycidyl polyether of adihydrie phenol having a 1,2-epoxy equivalency between 1.0 and 2.0 and a convertible alkylated urea-formaldehyde condensate soluble in n-butyl alcohol in admixture with about an added 0.2 to 5% by weight of the neutral salt of morpholine and p-toluenesulfonic acid, the composition containing a weight ratio of said polyether to said condensate of from about 90:10

to 30:70. 4. A composition which comprises a mixture.

of glycidyl polyether of a dihydric phenol having a 1,2-epoxy equivalency between 1.0 and 2.0 and a convertible urea-formaldehyde condensate containing about 15 to 40% by weight of the latter in admixture with about an added 0.2 to 5% by weight of the neutral salt of morpholine and a 12 substituted hydrocarbon containing as sole substituent group from 1 to 3 sulfonic acid groups.

5. A composition which comprises a mixture of glycidyl polyether of 2,2-bis(4-hydroxyphenyl)- propane having a 1,2-epoxy equivalency between 1.0 and 2.0 and a convertible urea-formaldehyde condensate containing about 15 to 40% by weight of the latter in admixture with about an added 0.2 to 5% by weight of the neutral salt of morpholine and p-toluenesulfonic acid.

6. A composition which comprises a mixture of glycidyl polyether of a dihydric phenol having a 1,2-epcxy equivalency between 1.0 and 2.0 and a convertible urea-formaldehyde condensate containing about 15 to 40% by weight of the latter in admixture with about an added 0.2 to 5% by weight of the neutral salt of diisopropylamine and p-toluenesulfonic acid.

'7. A composition which comprises a mixture of glycidyl polyether of 2,2-bis(4-hydroxyphenyl)- propane having a 1,2-epoxy equivalency between 1.0 and 2.0 and a convertible urea-formaldehyde condensate containing about 15 to 40% by weight of the latter in admixture with about an added 0.2 to 5% by weight of the neutral salt of diisoproplyamine and p-toluenesulfonic acid.

8. A composition which comprises a mixture of glycidyl polyether of a dihydric phenol having a 1,2-epoxy equivalency between 1.0 and 2.0 and a convertible urea-formaldehyde condensate containing about 15 to 40% by weight of the latter in admixture with about an added 0.2 to 5% by Weight of the neutral salt of triethylamine and p-toluenesulfonic acid.

9. A composition which comprises a mixture of glycidyl polyether of 2,2-bis(4-hydroxypheny1)- propane having a 1,2-epoxy equivalency between 1.0 and 2.0 and a convertible urea-formaldehyde condensate containing about 15 to 40% by weight of the latter in admixture with about an added 0.2 to 5% by weight of the neutral salt of triethylamine and p-toluenesulfonic acid.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,088,227 Battye et al. July 2'7, 1937 2,446,867 Cordier Aug. 10, 1948 2,512,996 Bixler June 2'7, 1950 2,591,539 Greenlee Apr. 1, 1952 OTHER REFERENCES Epon Resins, Paint, Oil and Chemical Review, vol. 113, No. 23, Nov. 9, 1950, pages 15-18. 48 and 49. 

1. A COMPOSITION ADAPTED TO CURE TO A HARD RESINOUS PRODUCT UPON BEING HEATED TO A TEMPERATURE ABOVE ABOUT 100* C. WHICH COMPRISES A MIXTURE OF GLYCIDYL POLYETHER OF A POLYHYDRIC PHENOL HAVING A 1,2-EPOXY EQUIVALENCY GREATER THAN 1.0 AND A CONVERTIBLE UREA-FORMALDEHYDE CONDENSATE IN ADMIXTURE WITH A SMALL AMOUNT OF A NEUTRAL SALT OF AN AMINE AND A SULFONIC ACID, SAID AMINE BEING A MEMBER OF THE GROUP CONSISTING OF MORPHOLINE, TRIETHYLAMINE, PYRIDINE, ANILINE DIISOPROPHYLAMINE, DIETHYLAMINE AND CETYLDIMETHYLAMINE. 